US7138179B2 - Method for preparing biodegradable polyester and itself prepared thereby - Google Patents
Method for preparing biodegradable polyester and itself prepared thereby Download PDFInfo
- Publication number
- US7138179B2 US7138179B2 US10/471,127 US47112704A US7138179B2 US 7138179 B2 US7138179 B2 US 7138179B2 US 47112704 A US47112704 A US 47112704A US 7138179 B2 US7138179 B2 US 7138179B2
- Authority
- US
- United States
- Prior art keywords
- monomer
- compound
- polymer
- dispersion solvent
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related, expires
Links
- 0 [2*:0]CC1=OOC([2*:0])C(=O)O1 Chemical compound [2*:0]CC1=OOC([2*:0])C(=O)O1 0.000 description 4
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
wherein R1 and R2 are a hydrogen or a C1–C4 alkyl group;
HO—C(═O)—(CH2)n—(O═)C—OH [Formula II]
wherein n is 1 to 8:
H—O—(CH2)m—O—H [Formula III]
wherein m is 2 to 8;
R3(OH)x [Formula IV]
wherein x is 2 to 6; and R3 is a saturated C1–C8 hydrocarbon or an ether (—R—O—R—); and
H—O—{(CH2CH2)yO}z—H [Formula V]
- (1) to be an organic compound in which the polymer has no solubility;
- (2) to be an organic compound in which the monomer has a solubility of less than 5%;
- (3) to be chemically inert with the monomer;
- (4) to have a viscosity of 1 to 300 cSt at 25° C.; and
- (5) to have a lower specific density of 0.85 to 1.25 than the polymer. Examples of the preferred dispersion solvent may include alkyl/aryl-substituted siloxane compounds (e.g., poly(dimethylsiloxane), poly(phenyl-methylsiloxane), etc.) and long-chained saturated hydrocarbons (e.g. liquid paraffin).
wherein R1 and R2 are a hydrogen or a C1–C4 alkyl group;
HO—C(═O)—(CH2)n—(O═)C—OH [Formula II]
wherein n is 1 to 8;
H—O—(CH2)m—O—H [Formula III]
wherein m is 2 to 8;
R3(OH)x [Formula IV]
wherein x is 2 to 6; and R3 is a saturated C1–C8 hydrocarbon or an ether (—R—O—R—); and
H—O—{(CH2CH2)yO}z—H [Formula V]
For linear polylactide (PLLA), [η]=4.41×10−4 ·M w 0.72 (dl/g)
For star-like (branched) PLLA, [η]=2.04×10−4 ·M w 0.72 (dl/g)
TABLE 1 |
Examples 2 to 10 |
Dispersion medium |
Monomer | Monomer/ | particle |
Ingredi- | Ingredient | B/ | volume | Dispersion | Molecular | Size | Δ HTm | Re- | ||||
ent A | B | (A + B) | type | viscosity | (ml) | medium | weight | Shape | (μm) | (J/g) | marks | |
2 | LLA | — | 0 | Polydimethylsiloxane | 200 cSt | 500 | 20% | 370,000 | amorphous | 20 | 87.6 | FIG. 2 | |
3 | LLA | — | 0% | Polyphenylmethylsiloxane | 10 cSt | 500 | 10% | 400,000 | spherical | 2 | 93.3 | FIG. | |
4 © | |||||||||||||
4 | LLA | — | 0% | Polydimethylsiloxane | 10 cSt | 500 | 80% | 740,000 | spherical | 70 | 81.0 | ||
5 | LLA | Er | 0.2% | Polydimethylsiloxane | 10 cSt | 500 | 60% | 760,000 | spherical | 25 | 89.4 | ||
6 | LLA | — | 0% | Liguid Paraffin | 30 cSt | 500 | 20% | 480,000 | spherical | 110 | 76.6 | ||
7 | GA | — | 0% | Polydimethylsiloxane | 10 cSt | 500 | 40% | 680,000 | spherical | 50 | 105 | ||
8 | LA | GA | 20% | Polydimethylsiloxane | 10 cSt | 500 | 40% | 560,000 | spherical | 15 | 56.1 | FIG. 3 | |
9 | LLA | CL | 10% | Polydimethylsiloxane | 10 cSt | 500 | 10% | 280,000 | spherical | 5 | 42.3 | ||
10 | LLA | Er, | 5% | Polydimethylsiloxane | 10 cSt | 500 | 40% | 440,000 | spherical | 35 | 47.8 | ||
SA, | |||||||||||||
EG | |||||||||||||
Note: | |||||||||||||
1) LLA = L-lactide | |||||||||||||
GA = Glycolide | |||||||||||||
CL = Caprolactone | |||||||||||||
Er = Pentaerithritol | |||||||||||||
SA = Succinic acid | |||||||||||||
EG = Ethyleneglycol | |||||||||||||
2) Reduced molecular weight calculated from intrinsic viscosity. | |||||||||||||
Examples 5, 8, 9 and 10: star-like PLLA reduction equation was applied. | |||||||||||||
3) Particle type and size: observed with SEM (FIGS. 1, 2 and 3) | |||||||||||||
Size: average particle size | |||||||||||||
4) DSC measurement (FIG. 4) |
TABLE 2 |
Comparative Example 1, 2 and 3 |
Dispersion medium |
Monomer | Monomer/ | particle |
Ingredient | Ingredient | B/ | vis- | Volume | Dispersion | Molecular | Size | Δ HTm | ||||
A | B | (A + B) | type | cosity | (ml) | medium | weight | Shape | (μm) | (J/g) | Remarks | |
1 | LLA | — | 0% | Polydimethylsiloxane | 500 cSt | 500 | 40% | 95,000 | amorphous | 0.5↓ | 79.5 | Yield |
(random - | rate: | |||||||||||
shaped) | below | |||||||||||
30%, | ||||||||||||
difficult | ||||||||||||
to collect | ||||||||||||
2 | LLA | — | 0% | Polydimethylsiloxane | 10 cSt | 500 | 90% | 250,000 | — | — | 57.1 | Impossible |
to form | ||||||||||||
monomer | ||||||||||||
drop(FIG. | ||||||||||||
4) | ||||||||||||
3 | LLA | — | 0% | 590,000 | 39.1 | Bulk polym- | ||||||
erization | ||||||||||||
Claims (19)
HO—C(═O)—(CH2)n—(O═)C—OH [Formula II]
H—O—(CH2)m—O—H [Formula III]
R3(OH)x [Formula IV]
H—O—{(CH2CH2)yO}z—H. [Formula V]
HO—C(═O)—(CH2)n—(O═)C—OH [Formula II]
H—O—(CH2)m—O—H [Formula III]
R3(OH)x [Formula IV]
H—O—{(CH2CH2)yO}z—H [Formula V]
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020010012674A KR100354828B1 (en) | 2001-03-12 | 2001-03-12 | Method for preparing biodegradable polyester and itself prepared thereby |
KR2001/12674 | 2001-03-12 | ||
PCT/KR2002/000264 WO2002072663A1 (en) | 2001-03-12 | 2002-02-20 | Method for preparing biodegradable polyester and itself prepared thereby |
Publications (2)
Publication Number | Publication Date |
---|---|
US20040138333A1 US20040138333A1 (en) | 2004-07-15 |
US7138179B2 true US7138179B2 (en) | 2006-11-21 |
Family
ID=19706790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/471,127 Expired - Fee Related US7138179B2 (en) | 2001-03-12 | 2002-02-20 | Method for preparing biodegradable polyester and itself prepared thereby |
Country Status (4)
Country | Link |
---|---|
US (1) | US7138179B2 (en) |
EP (1) | EP1373357A4 (en) |
KR (1) | KR100354828B1 (en) |
WO (1) | WO2002072663A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060153786A1 (en) * | 2004-12-10 | 2006-07-13 | Talima Therapeutics, Inc. | Compositions and methods for treating conditions of the nail unit |
US20060275230A1 (en) * | 2004-12-10 | 2006-12-07 | Frank Kochinke | Compositions and methods for treating conditions of the nail unit |
US20100217200A1 (en) * | 2003-06-16 | 2010-08-26 | Ethicon Endo-Surgery, Inc. | Injection Port with Applier |
US8864717B2 (en) | 2003-06-16 | 2014-10-21 | Ethicon Endo-Surgery, Inc. | Subcutaneous self attaching injection port with integral moveable retention members |
US9375558B2 (en) | 2013-03-14 | 2016-06-28 | Hallux, Inc. | Method of treating infections, diseases or disorders of nail unit |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8980300B2 (en) | 2004-08-05 | 2015-03-17 | Advanced Cardiovascular Systems, Inc. | Plasticizers for coating compositions |
US8889823B2 (en) | 2009-07-21 | 2014-11-18 | Abbott Cardiovascular Systems Inc. | Method to make poly(L-lactide) stent with tunable degradation rate |
US9889238B2 (en) * | 2009-07-21 | 2018-02-13 | Abbott Cardiovascular Systems Inc. | Biodegradable stent with adjustable degradation rate |
US8709070B2 (en) | 2011-05-10 | 2014-04-29 | Abbott Cardiovascular Systems Inc. | Bioabsorbable scaffold with particles providing delayed acceleration of degradation |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804691A (en) | 1987-08-28 | 1989-02-14 | Richards Medical Company | Method for making a biodegradable adhesive for soft living tissue |
WO1994011441A1 (en) | 1992-11-06 | 1994-05-26 | Rijksuniversiteit Te Groningen | Rubber-modified polylactide and/or glycolide composition |
US5683723A (en) * | 1991-06-28 | 1997-11-04 | Rhone-Poulenc Rorer S.A. | Nanoparticles based on a polyoxyethelene and polyactic acid block copolymer |
US5702717A (en) * | 1995-10-25 | 1997-12-30 | Macromed, Inc. | Thermosensitive biodegradable polymers based on poly(ether-ester)block copolymers |
WO2001060425A1 (en) | 2000-02-15 | 2001-08-23 | Jvs-Polymers Oy | Biodegradable material |
US6297350B1 (en) * | 1997-06-06 | 2001-10-02 | Ferring Gmbh | Process for the preparation of copolyesters |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4605730A (en) * | 1982-10-01 | 1986-08-12 | Ethicon, Inc. | Surgical articles of copolymers of glycolide and ε-caprolactone and methods of producing the same |
US4804461A (en) * | 1987-10-22 | 1989-02-14 | Gerhard Heinrich | Process for recovering barite from drilling muds |
US5412067A (en) * | 1993-05-10 | 1995-05-02 | Mitsui Toatsu Chemicals, Inc. | Preparation process of polyester |
JP3557050B2 (en) * | 1995-09-07 | 2004-08-25 | 三井化学株式会社 | Bioabsorbable polymer and method for producing the same |
US6068920A (en) * | 1997-09-04 | 2000-05-30 | Mitsui Chemicals, Inc. | Random-block copolymer and monofilament thereof |
KR100348717B1 (en) * | 1999-10-08 | 2002-08-14 | 주식회사 삼양사 | Star-Shaped Glycolide/ε-Caprolactone Copolymers and Process for Their Preparation |
-
2001
- 2001-03-12 KR KR1020010012674A patent/KR100354828B1/en not_active IP Right Cessation
-
2002
- 2002-02-20 US US10/471,127 patent/US7138179B2/en not_active Expired - Fee Related
- 2002-02-20 EP EP02700869A patent/EP1373357A4/en not_active Withdrawn
- 2002-02-20 WO PCT/KR2002/000264 patent/WO2002072663A1/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4804691A (en) | 1987-08-28 | 1989-02-14 | Richards Medical Company | Method for making a biodegradable adhesive for soft living tissue |
US5683723A (en) * | 1991-06-28 | 1997-11-04 | Rhone-Poulenc Rorer S.A. | Nanoparticles based on a polyoxyethelene and polyactic acid block copolymer |
WO1994011441A1 (en) | 1992-11-06 | 1994-05-26 | Rijksuniversiteit Te Groningen | Rubber-modified polylactide and/or glycolide composition |
US5702717A (en) * | 1995-10-25 | 1997-12-30 | Macromed, Inc. | Thermosensitive biodegradable polymers based on poly(ether-ester)block copolymers |
US6297350B1 (en) * | 1997-06-06 | 2001-10-02 | Ferring Gmbh | Process for the preparation of copolyesters |
WO2001060425A1 (en) | 2000-02-15 | 2001-08-23 | Jvs-Polymers Oy | Biodegradable material |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8864717B2 (en) | 2003-06-16 | 2014-10-21 | Ethicon Endo-Surgery, Inc. | Subcutaneous self attaching injection port with integral moveable retention members |
US8758303B2 (en) | 2003-06-16 | 2014-06-24 | Ethicon Endo-Surgery, Inc. | Injection port with applier |
US8764713B2 (en) | 2003-06-16 | 2014-07-01 | Ethicon Endo-Surgery, Inc. | Method of repositioning an injection port |
US20100217200A1 (en) * | 2003-06-16 | 2010-08-26 | Ethicon Endo-Surgery, Inc. | Injection Port with Applier |
US8354095B2 (en) | 2004-12-10 | 2013-01-15 | Hallux, Inc. | Compositions and methods for treating conditions of the nail unit |
US8591870B2 (en) | 2004-12-10 | 2013-11-26 | Hallux, Inc. | Compositions and methods for treating conditions of the nail unit |
US20060275230A1 (en) * | 2004-12-10 | 2006-12-07 | Frank Kochinke | Compositions and methods for treating conditions of the nail unit |
US8747820B2 (en) | 2004-12-10 | 2014-06-10 | Hallux, Inc. | Methods for treating conditions of the nail unit |
US20060153786A1 (en) * | 2004-12-10 | 2006-07-13 | Talima Therapeutics, Inc. | Compositions and methods for treating conditions of the nail unit |
US20080132442A1 (en) * | 2004-12-10 | 2008-06-05 | Kochinke Frank M | Compositions and methods for treating conditions of the nail unit |
US9446009B2 (en) | 2004-12-10 | 2016-09-20 | Hallux, Inc. | Methods for treating conditions of the nail unit |
US9375558B2 (en) | 2013-03-14 | 2016-06-28 | Hallux, Inc. | Method of treating infections, diseases or disorders of nail unit |
US9498612B2 (en) | 2013-03-14 | 2016-11-22 | Hallux, Inc. | Method of treating infections, diseases or disorders of nail unit |
US10456568B2 (en) | 2013-03-14 | 2019-10-29 | Hallux, Inc. | Method of treating infections, diseases or disorders of nail unit |
Also Published As
Publication number | Publication date |
---|---|
US20040138333A1 (en) | 2004-07-15 |
EP1373357A1 (en) | 2004-01-02 |
KR20010044625A (en) | 2001-06-05 |
EP1373357A4 (en) | 2005-01-19 |
KR100354828B1 (en) | 2002-10-05 |
WO2002072663A1 (en) | 2002-09-19 |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: CHEMICAL & MEDICAL RESEARCH CO., LTD., KOREA, REPU Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KIM, KYEONG AH;SON, BYUNG KUN;JEON, YONG GUN;REEL/FRAME:014995/0580 Effective date: 20031119 |
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FEPP | Fee payment procedure |
Free format text: PAT HOLDER CLAIMS SMALL ENTITY STATUS, ENTITY STATUS SET TO SMALL (ORIGINAL EVENT CODE: LTOS); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
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FPAY | Fee payment |
Year of fee payment: 4 |
|
REMI | Maintenance fee reminder mailed | ||
LAPS | Lapse for failure to pay maintenance fees | ||
STCH | Information on status: patent discontinuation |
Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362 |
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FP | Lapsed due to failure to pay maintenance fee |
Effective date: 20141121 |